CN109293789A - A kind of alpha-cyclodextrin modified starch paste and preparation method thereof - Google Patents
A kind of alpha-cyclodextrin modified starch paste and preparation method thereof Download PDFInfo
- Publication number
- CN109293789A CN109293789A CN201811193613.6A CN201811193613A CN109293789A CN 109293789 A CN109293789 A CN 109293789A CN 201811193613 A CN201811193613 A CN 201811193613A CN 109293789 A CN109293789 A CN 109293789A
- Authority
- CN
- China
- Prior art keywords
- starch
- parts
- cyclodextrin
- alpha
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/11—Starch or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention relates to weaving modified starch size technology, specially a kind of immobilized starch of alpha-cyclodextrin and preparation method thereof, it is characterised in that the material quality of the starch forms number are as follows: 50 parts of cornstarch；50 parts of alpha-cyclodextrin；20 parts of malic acid；7.5 parts of sodium hypophosphite；300 parts of deionized water.The technical solution that the present invention solves the preparation method technical problem is, design a kind of preparation method of immobilized starch of alpha-cyclodextrin (CS- α CD), the preparation method is using the material quality composition of acetylation cornstarch of the present invention and following processing step: (1) the native cornstarch of the number, starch suspension is made in alpha-cyclodextrin and 200 parts of deionized waters, it is transferred in 500mL three-necked flask, it is placed in 85 DEG C of water-baths, connect condensing unit, Heat Gelatinization 30min, the solution of 100 parts of malic acid containing the number and sodium hypophosphite is then added by constant pressure funnel, it stirs evenly, it is taken out after mixture is transferred to 120 DEG C of reaction 2h of baking oven.(2) take out and crush after reaction, be washed with deionized twice, then with 75% twice of ethanol washing, centrifugation drying obtain the immobilized starch of sample alpha-cyclodextrin, that is, CS- α CD.
Description
Technical field
The present invention relates to weaving modified starch size technology, the immobilized starch of specially a kind of alpha-cyclodextrin and its preparation side
Method.
Background technique
Main slurry of the starch as warp yarn sizing, source is very extensive, and cheap, but size mixing formality trouble, starching
Performance can not be satisfactory.The appearance of PVA, solves the sizing of hydrophobic fibre, and brilliant filming performance is recognized
For the revolution for being warp yarn sizing.But PVA is difficult to degrade and pollute the environment, it is considered to be unclean slurry.Due to starch
It is resourceful, it is easy to degrade, people can chemically or physically be denaturalized starch using the feature in starch polymer structure,
Improve the practical performance of starch.A thinking for replacing PVA is exactly to carry out denaturation treatment to starch, to reach independent or and propylene
Acids slurry is used in mixed way, and gets rid of the purpose of PVA.
Cyclodextrin (abbreviation CD) is generally made of 6-8 glucose molecule, and shaped like a cylinder, surface is dispersed with molecule
Numerous reactive hydroxyls, it is water-soluble strong, be a kind of natural oligosaccharides, structure is similar to starch, in conjunction with starch after can
It is water-soluble to form a kind of holding, and does not destroy the novel starch of its degradability.
In research at home and abroad, majority research is partial to gather to such as polystyrene, polylactic acid, shell by beta-cyclodextrin is immobilized
In the synthesis such as sugar and cellulose or natural macromolecular material, but using starch as carrier, the immobilized starch slurry yarn material of cyclodextrin is prepared
The research of aspect is but very rare.Moreover, research before this is confined to beta-cyclodextrin to the immobilized of a variety of materials mostly, and
Immobilized aspect in relation to alpha-cyclodextrin on the natural macromoleculars such as starch and chitosan rarely has research.Based on this, alpha-cyclodextrin
(α-CD) can be immobilized on starch molecule by way of crosslinking, forms alpha-cyclodextrin chemically modifying polysaccharides derivative, is allowed to
It has the property of starch and cyclodextrin concurrently, including has many advantages, such as good mechanical performance, chemical stability and chemical adjustability.Together
When cyclodextrin introducing, can also largely change the physicochemical property of starch itself, reduction, inherent viscosity such as crystallinity
It is reduced with apparent viscosity, the enhancing of hydratability and the raising of ageing resistance etc., so as to improve the slashing performance of starch itself.
Its degradation property is had studied simultaneously, alpha-cyclodextrin and starch are all easy to degrade, and the immobilized starch of alpha-cyclodextrin is a kind of with potential
Biodegradable graft starch.
Summary of the invention
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve is: providing a kind of immobilized starch of alpha-cyclodextrin
(CS- α CD) and preparation method thereof.The physicochemical property of the starch has larger improvement, solubility, expansive force and paste liquid compared to CS
Transparency improves, and intrinsic viscosity and apparent viscosity reduce, and rheological property improves；Crystallinity reduces, and reinforces with the active force of water, molten
Swollen performance and paste transparency improve；It pastes liquid simultaneously to stablize, anti-aging property enhancing.Compared with CS, the slashing performance of CS- α CD has
It is improved.The starch preparation method reaction efficiency is high, reaction condition mitigates, easy to control, repeatable convenient for product separation, process
Height, and pollution-free in production process, it is highly-safe the features such as.
The technical solution that the present invention solves the starch technical problem is to design a kind of immobilized starch of alpha-cyclodextrin (CS- α
CD), it is characterised in that the material quality of the starch forms number are as follows: 50 parts of cornstarch；50 parts of alpha-cyclodextrin；Malic acid 20
Part；7.5 parts of sodium hypophosphite；300 parts of deionized water.
The technical solution that the present invention solves the preparation method technical problem is to design a kind of immobilized starch of alpha-cyclodextrin
The preparation method of (CS- α CD), the preparation method using acetylation cornstarch of the present invention material quality composition and it is following
Processing step:
(1) starch suspension is made in the native cornstarch of the number, alpha-cyclodextrin and 200 parts of deionized waters, shifted
It into 500mL three-necked flask, is placed in 85 DEG C of water-baths, connects condensing unit, Heat Gelatinization 30min then passes through constant pressure
The solution of 100 parts of malic acid containing the number and sodium hypophosphite is added in dropping funel, stirs evenly, mixture is transferred to
It is taken out after 120 DEG C of reaction 2h of baking oven.
(2) take out and crush after reaction, be washed with deionized twice, then with 75% twice of ethanol washing, from
Heart drying obtains the immobilized starch of sample alpha-cyclodextrin, that is, CS- α CD.
Detailed description of the invention
Fig. 1 is a kind of Raman comparison diagram of embodiment and CS of CS- α CD of the present invention；
Fig. 2 is a kind of scanning electron microscope image of embodiment and CS of CS- α CD of the present invention；
Fig. 3 is a kind of X-ray diffraction spectrogram of embodiment and CS of CS- α CD of the present invention；
Fig. 4 is a kind of anti -precipitability figure of embodiment and CS of CS- α CD of the present invention；
Specific embodiment:
The present invention is further discussed below below with reference to examples and drawings.
A kind of immobilized starch of alpha-cyclodextrin (abbreviation CS- α CD, referring to Fig. 1-2) that the present invention designs, it is characterised in that the shallow lake
The material quality of powder forms number are as follows: 50 parts of cornstarch；50 parts of alpha-cyclodextrin；20 parts of malic acid；7.5 parts of sodium hypophosphite；It goes
300 parts of ionized water.
The structural characterization and analysis of physical and chemical property of CS- α CD of the present invention is following (referring to Fig. 1-2).
Fig. 1 is a kind of Raman comparison diagram of embodiment and CS of CS- α CD of the present invention, and CS macromolecular skeleton methylene is symmetrical
Stretching vibration vsC-H is in Raman spectrum 2931cm-1Nearby there is extremely strong scattering.In addition, CS is in 1150-1050cm-1There are hydroxyls at place
Carbon-oxygen bond stretching vibration vC-ORAM spectral peak.In contrast, the RAM spectrum of CS- α CD has significant change.CS- α CD is in 2931cm-1
The signal at place is reinforced, and is in because being introduced into CS- α CD molecule as MA cross-linking reaction has carried out a large amount of methylene
1150-1050cm-1Region vO-HPeak intensity should weaken, but continuing to increase due to c h bond in the reaction, so that the peak value at this
Increase.CS- α CD is in 1700cm-1Neighbouring vC=OThe RAM signal enhancing of stretching vibration, since MA introduces α-CD as crosslinking agent
Constantly have ester group generation during CS- α CD, and with the progress of reaction, part MA and starch reaction, form monoesters, make hydroxyl,
The content of ester group is continuously increased, therefore the stretching vibration of carbonyl is obvious.
Fig. 2 is respectively ative starch, the scanning electron microscope (SEM) photograph of CS- α CD particle.Corn is former it can be seen from Fig. 2 scanning electron microscope (SEM) photograph
Shape of starch granules is mostly round, angular, polygon etc., smooth surface, regular.Compared with ative starch, CS- α CD particle
Surface is very coarse, is covered with tiny hole, and particle size is greater than native corn starch, and internal structure is loose hollow and exists
A large amount of holes.In the synthesis process, when corn starch solution is sufficiently heated, its form is destroyed, starch molecule chain link it
Between active force increase in cross-linking process, under the connection of malic acid, originally between separated cornstarch and α-CD particle
Segment be cross-linked with each other, form new bulky grain.
Fig. 3 is a kind of X-ray diffraction spectrogram of embodiment and CS of CS- α CD of the present invention, from figure 3, it can be seen that CS- α CD
Diffraction peak type compared with CS, have occurred apparent variation, diffracted intensity weakens, and peak shape is converted from spike to dispersivity, shows
Crystallinity decline.XRD's observation indicate that, for cornstarch during Heat Gelatinization, crystalline region is by serious broken
It is bad, due to introducing MA and α-CD in starch, the original crystal region of ative starch is destroyed, starch granules structure is destroyed, and
New bulky grain is formed under the action of crosslinking agent, crystallinity is declined, and it is loosely organized, be conducive to improve its hydrophily.
The analysis of Fig. 1, Fig. 2 and Fig. 3 the result shows that, preparation method of the present invention is successfully immobilized by α-CD by crosslinking agent of MA
Onto starch molecule, by infrared spectroscopy can be obvious be seen that there is most carboxylic acid group and be introduced in CS- α CD, sweep
It retouches electron microscope observation discovery CS- α CD rough surface, short texture, particle and is greater than cornstarch, largely change
The physicochemical property of CS- α CD, such as improves dissolubility, dilatancy, improves swelling character, rheological property, anti -precipitability and biochemistry
Degradability etc., and in the slashing performance that the raising of these performances is also CS- α CD is greatly improved compared to native cornstarch
In reason.
The present invention devises a kind of preparation method (abbreviation preparation method) of immobilized starch of alpha-cyclodextrin, the preparation side simultaneously
Method using the immobilized starch of alpha-cyclodextrin of the present invention material quality part array at following processing step: cornstarch 50
Part；50 parts of alpha-cyclodextrin；20 parts of malic acid；7.5 parts of sodium hypophosphite；300 parts of deionized water.
(1) starch suspension is made in the native cornstarch of the number, alpha-cyclodextrin and 200 parts of deionized waters, shifted
It into 500mL three-necked flask, is placed in 85 DEG C of water-baths, connects condensing unit, Heat Gelatinization 30min then passes through constant pressure
The solution of 100 parts of malic acid containing the number and sodium hypophosphite is added in dropping funel, stirs evenly, mixture is transferred to
It is taken out after 120 DEG C of reaction 2h of baking oven.
(2) take out and crush after reaction, be washed with deionized twice, then with 75% twice of ethanol washing, from
Heart drying obtains the immobilized starch of sample alpha-cyclodextrin, that is, CS- α CD.
The present invention is determined the degree of substitution of CS- α CD.The measurement of CS- α CD degree of substitution uses the hyperchromic method of methyl orange,
Measure the content and immobilized rate of α-CD in CS- α CD.
CS- α CD preparation method experimental instrument and equipment of the present invention includes: FA2004 type electronic analytical balance, DW-3 digital display electricity
Dynamic stirring, SYC thermostat water bath, GT16-3A table model high speed centrifuge, YLD-2000 electric heating constant-temperature blowing drying box, DFT-50
Type 50g portable universal pulverizer.Instrument and equipment used in the method for the present invention is routine instrument device, at low cost, easy to operate,
Technology maturation is suitable for industrial application.
In order to illustrate the raising of CS- α CD physicochemical property, the present invention tests the inherent viscosity of CS- α CD respectively, apparently glues
Degree, expansive force, solubility, transparency and anti -precipitability.Its test method is respectively as follows:
Inherent viscosity and apparent viscosity: dry starch sample is taken to be added in solvent dimethyl sulfoxide, configuration concentration is
The solution of 0.005g/mL crosses 0.2 μm of filter membrane.Use its inherent viscosity of dilution type detection of capillary tube viscosity, capillary inner diameter
0.61mm, 25 DEG C of measuring temperature；Sample apparent viscosity is measured using NDJ-79 type rotary viscosimeter, measuring temperature is 95 DEG C,
Gelatinized corn starch mass concentration is 6%.
Expansive force and solubility: configuration quality volume ratio is the starch aqueous suspensions 50mL of 2% (m/V), in 90 DEG C of thermostatted waters
The lower stirring gelatinization 30min of bath, pours into centrifuge tube for gelatinized corn starch, is centrifuged 20min under 3000r/min revolving speed.Supernatant is poured into
The plate of known quality, at 105 DEG C, drying to constant weight after 80 DEG C of drying liquids.Solubility is for supernatant dried object quality and always
The ratio of starch dry mass, expansive force are contained in gelatinized corn starch quality (expansion starch quality in centrifuge tube) after centrifugation and gelatinized corn starch
The ratio of starch dry mass.
Transparency: weighing 1.00g starch (in terms of starch on dry basis), and preparation mass fraction is 1.0% starch milk, in boiling water bath
30min is stirred in middle gelatinization, is cooled to room temperature, is adjusted with distilled water to original volume.Make reference with distilled water, uses Thermo
Helios- γ type ultra-violet and visible spectrophotometer surveys light transmittance at 620nm wavelength.Same sample is measured 3 times.
Anti -precipitability: weighing 1.00g sample, and 100mL distilled water is added, and preparing becomes the shallow lake that mass volume ratio is 1.0%
Powder cream, Heat Gelatinization and keeps the temperature 30min in boiling water bath, is cooled to room temperature, and takes 50mL to move into 50mL tool plug graduated cylinder, in 25-
30 DEG C of standings, record supernatant liquor volume at regular intervals.It is changed with time with supernatant liquor volume to indicate the solidifying of paste
Heavy property.
In order to compare inherent viscosity, apparent viscosity, expansive force, solubility, transparency and the anti -precipitability of CS Yu CS- α CD,
The present invention has done inherent viscosity, apparent viscosity, expansive force, solubility, transparency and anti -precipitability to CS and can test.Except in formula
CS- α CD uses CS, PVA205 substitution outer respectively, remaining condition is the same as CS- α CD.
In order to illustrate CS- α CD for the slashing performance of polyester cotton mixed yarn, the present invention is to the polyester cotton after CS- α CD starching
The ultimate strength, extension at break and hairiness index of (T/C 65/35) blended roving are tested, starching and test method
Are as follows:
The slurries of 6% concentration are made of distilled water, starch size, are heated to 95 DEG C, keep the temperature one hour, for use.Upper sizing
Line is that the blended spun yarn T/C of polyester cotton is 65/35, and special number is 18.4t.It is carried out on the full-automatic sample single end sizing machine of ASS3000 type
Starching experiment, sizing machine major parameter are as follows: 90 DEG C of sizing temperature, speed 35m/min, 80 DEG C of oven temperature, squeezing roller pressure
0.2mpa is to get to the sizing that can be tested and testing its ultimate strength, extension at break and hairiness index.
In order to compare the slashing performance of CS- α CD Yu CS, PVA-205 slurries, the present invention is respectively to CS, PVA-205 starching
The slashing performance of polyester cotton (T/C 65/35) blended roving afterwards is tested.Except CS- α CD uses CS, PVA- respectively in formula
205 substitutions are outer, remaining condition is the same as CS- α CD.
In order to illustrate the raising of the biodegradability of CS- α CD, the present invention tests the degradation property of CS- α CD.
With the COD COD of potassium dichromate method measurement sampleCr, with the biochemical oxygen demand (BOD) of iodimetric titration biochemical measurement sample
BOD5, using 1g/L starch sample solution as water sample in measurement, its COD is measured by 5 times of dilutionCrValue dilutes 100 times to measure
Its BOD5Value.The biological degradability of sample is with B/C ratio, i.e. BOD5 and CODCrRatio indicate.
In order to compare the degradation property of CS, α-CD, CS- α CD and PVA205, the present invention is respectively to CS, α-CD and PVA205
Degradation property test is done.In addition to CS- α CD uses CS, PVA205 to substitute respectively in formula, remaining condition is the same as CS- α CD.
Specific embodiments of the present invention are given below.Specific embodiment is merely to present invention be described in more detail, no
Limit claim of the invention.
Embodiment 1
(1) 50g starch, 50g alpha-cyclodextrin and 200mL distilled water are weighed in 500mL three neck round bottom flask, in 85 DEG C of water
Heat Gelatinization 30min in bath is then added the 100mL solution containing 20g malic acid, 7.5g sodium hypophosphite respectively, stirs evenly
Afterwards, mixture is transferred to 120 DEG C of reaction 2h of baking oven.
(2) it takes out and crushes after reaction, distilled twice of water washing with 100mL, 75% ethanol solution 100mL is washed 2 times.
Immobilized validity check: relevant parameter is measured referring to the measuring method of CS- α CD degree of substitution in upper section.The present embodiment warp
The degree of substitution and reaction efficiency data of calculating are listed in table 1, and structural characterization is referring to Fig. 1 and Fig. 2.
Embodiment 2
(1) 50g starch, 25g alpha-cyclodextrin and 200mL distilled water are weighed in 500mL three neck round bottom flask, in 85 DEG C of water
Heat Gelatinization 30min in bath is then added the 100mL solution containing 20g malic acid, 7.5g sodium hypophosphite respectively, stirs evenly
Afterwards, mixture is transferred to 120 DEG C of reaction 2h of baking oven.
(2) it takes out and crushes after reaction, distilled twice of water washing with 100mL, 75% ethanol solution 100mL is washed 2 times.
The immobilized rate that the present embodiment is computed is listed in table 1.
Embodiment 3
(1) 50g starch, 50g alpha-cyclodextrin and 200mL distilled water are weighed in 500mL three neck round bottom flask, in 85 DEG C of water
The 100mL solution containing 20g malic acid, 5g sodium hypophosphite respectively is then added in Heat Gelatinization 30min in bath, after mixing evenly,
Mixture is transferred to 120 DEG C of reaction 2h of baking oven.
(2) it takes out and crushes after reaction, distilled twice of water washing with 100mL, 75% ethanol solution 100mL is washed 2 times.
The immobilized rate that the present embodiment is computed is listed in table 1.
Embodiment 4
(1) 50g starch, 50g alpha-cyclodextrin and 200mL distilled water are weighed in 500mL three neck round bottom flask, in 85 DEG C of water
Heat Gelatinization 30min in bath is then added the 100mL solution containing 20g malic acid, 7.5g sodium hypophosphite respectively, stirs evenly
Afterwards, mixture is transferred to 110 DEG C of reaction 2h of baking oven.
(2) it takes out and crushes after reaction, distilled twice of water washing with 100mL, 75% ethanol solution 100mL is washed 2 times.
The immobilized rate that the present embodiment is computed is listed in table 1.
Embodiment 5
(1) 50g starch, 50g alpha-cyclodextrin and 200mL distilled water are weighed in 500mL three neck round bottom flask, in 85 DEG C of water
Heat Gelatinization 30min in bath is then added the 100mL solution containing 15g malic acid, 7.5g sodium hypophosphite respectively, stirs evenly
Afterwards, mixture is transferred to 120 DEG C of reaction 2h of baking oven.
(2) it takes out and crushes after reaction, distilled twice of water washing with 100mL, 75% ethanol solution 100mL is washed 2 times.
The immobilized rate that the present embodiment is computed is listed in table 1.
1 embodiment 1 of table is compared with the grafting parameters of embodiment 2~5
Embodiment 6
CS- α CD is taken to be added in solvent dimethyl sulfoxide, configuration concentration is the solution of 0.005g/mL, crosses 0.2 μm of filter membrane.Make
With its inherent viscosity of dilution type detection of capillary tube viscosity, capillary inner diameter 0.61mm, 25 DEG C of measuring temperature；Use NDJ-79 type
Rotary viscosimeter measures sample apparent viscosity, and measuring temperature is 95 DEG C, and gelatinized corn starch mass concentration is 6%.
Test result is shown in Table 2.
Comparative example 1
Have compared to CS and significantly reduce in order to illustrate the intrinsic viscosity and apparent viscosity of CS- α CD, the present invention is simultaneously
The test of inherent viscosity and apparent viscosity has been done to CS.In addition to CS- α CD is substituted with CS in formula, remaining is the same as embodiment 6.
Test result is shown in Table 2.
2 embodiment 6 of table, 1 inherent viscosity of comparative example are compared with apparent viscosity parameter
| Inherent viscosity (mLg-1) | Apparent viscosity (mPas) | |
| Embodiment 6 | 170.19 | 26.3 |
| Comparative example 1 | 168.45 | 561.5 |
Embodiment 7
Configuration quality volume ratio is the CS- α CD aqueous suspensions 50mL of 2% (m/V), and gelatinization is stirred under 90 DEG C of waters bath with thermostatic control
CS- α CD paste is poured into centrifuge tube, is centrifuged 20min under 3000r/min revolving speed by 30min.Supernatant is poured into known quality
Plate, at 105 DEG C, drying to constant weight after 80 DEG C of drying liquids.Solubility is that supernatant dried object quality and total CS- α CD do matter
The ratio of amount, expansive force are that gelatinized corn starch quality (expansion starch quality in centrifuge tube) and starch contained therein in CS- α CD paste are dry after being centrifuged
The ratio of quality.
Test result is shown in Table 3.
Comparative example 2
Have significant improvement in order to illustrate the expansive force and solubility of CS- α CD compared to CS, the present invention is simultaneously to CS
The test of expansive force and solubility is done.In addition to CS- α CD is substituted with CS in formula, remaining is the same as embodiment 7.
Test result is shown in Table 3.
3 embodiment 7 of table, 2 expansive force of comparative example are compared with solubility parameter
| Expansive force (gg-1) | Solubility (%) | |
| Embodiment 7 | 27.03 | 37.68 |
| Comparative example 2 | 20.45 | 14.9 |
Embodiment 8
1.00gCS- α CD is weighed, preparation mass fraction is 1.0% starch milk, and gelatinization stirring 30min, cold in boiling water bath
But it to room temperature, is adjusted with distilled water to original volume.Make reference with distilled water, uses Thermo Helios- γ type UV, visible light
Light spectrophotometer surveys light transmittance at 620nm wavelength.Same sample is measured 3 times.
Test result is shown in Table 4.
Comparative example 3
Transparency in order to illustrate CS- α CD is greatly improved compared to CS, and the present invention has done transparency to CS simultaneously
Test.In addition to CS- α CD is substituted with CS in formula, remaining is the same as embodiment 8.
Test result is shown in Table 4.
4 embodiment 8 of table, 3 transparency parameter of comparative example compare
| Transparency | |
| Embodiment 8 | 28.38 |
| Comparative example 3 | 12.06 |
Embodiment 9
1.00g sample is weighed, 100mL distilled water is added, preparing becomes the starch milk that mass volume ratio is 1.0%, in boiling
Heat Gelatinization and 30min is kept the temperature in water-bath, is cooled to room temperature, taken 50mL to move into 50mL tool plug graduated cylinder, stood at 25-30 DEG C,
Supernatant liquor volume is recorded at regular intervals.It is changed with time with supernatant liquor volume to indicate the retrogradation property of paste.
Test result is shown in Fig. 4.
Comparative example 4
Anti -precipitability in order to illustrate CS- α CD is greatly improved compared to CS, and it is anticoagulant heavy that the present invention has simultaneously been CS
The test of property.In addition to CS- α CD is substituted with CS in formula, remaining is the same as embodiment 9.
Test result is shown in Fig. 4.
Embodiment 10
The slurries of 6% concentration are made of distilled water, starch size, are heated to 95 DEG C, keep the temperature one hour, for use.Upper sizing
Line is that the blended spun yarn T/C of polyester cotton is 65/35, and special number is 18.4t.It is carried out on the full-automatic sample single end sizing machine of ASS3000 type
Starching experiment, sizing machine major parameter are as follows: 90 DEG C of sizing temperature, speed 35m/min, 80 DEG C of oven temperature, squeezing roller pressure
0.2mpa is to get to the sizing that can be tested and testing its ultimate strength, extension at break and hairiness index.
Test result is shown in Table 5.
Comparative example 5
In order to compare the slashing performance of CS- α CD Yu CS, PVA-205 slurries, the present invention is respectively to CS, PVA-205 starching
The slashing performance of polyester cotton (T/C 65/35) blended roving afterwards is tested.Except CS- α CD uses CS, PVA- respectively in formula
205 substitutions are outer, remaining is the same as embodiment 10.
Test result is shown in Table 5.
5 embodiment 10 of table, 5 transparency parameter of comparative example compare
| It is broken enhancing rate (%) | It extends slip (%) | Filoplume reduced rate (%) | |
| CS-αCD | 18.54 | 18.57 | 89.04 |
| CS | 3.67 | 12.94 | 78.64 |
| PVA-205 | 30.29 | 27.43 | 92.56 |
Embodiment 11
With the COD COD of potassium dichromate method measurement sampleCr, with the biochemical oxygen demand (BOD) of iodimetric titration biochemical measurement sample
BOD5, using 1g/L starch sample solution as water sample in measurement, its COD is measured by 5 times of dilutionCrValue dilutes 100 times to measure
Its BOD5Value.The biological degradability of sample is with B/C ratio, i.e. BOD5 and CODCrRatio indicate.
Test result is shown in Table 6.
Comparative example 6
In order to compare the degradation property of CS, α-CD, CS- α CD and PVA205, the present invention is respectively to CS, α-CD and PVA205
Degradation property test is done.In addition to CS- α CD uses CS, PVA205 to substitute respectively in formula, remaining is the same as case study on implementation 11.
Test result is shown in Table 6.
6 embodiment 11 of table, 6 transparency parameter of comparative example compare
| BOD5(mg/g) | CODcr(mg/g) | B/C | |
| CS-αCD | 51.328 | 64.629 | 0.794 |
| CS | 42.652 | 66.527 | 0.641 |
| α-CD | 48.026 | 64.388 | 0.746 |
| PVA-205 | 1.782 | 131.682 | 0.014 |
The physicochemical property of CS- α CD has larger improvement compared to CS, and solubility, expansive force and paste liquid transparency improve, special
Property viscosity and apparent viscosity reduce, rheological property improve；Crystallinity reduces, and reinforces with the active force of water, and swelling behavior and paste are saturating
Lightness improves；It pastes liquid simultaneously to stablize, anti-aging property enhancing.
Compared with CS, the slashing performance of CS- α CD increases, and the raising of physicochemical property is that CS- α CD slashing performance changes
Kind internal factor.Since CS- α CD contains group similar with polyester fiber macromolecular structure with cotton fiber, between cotton fiber
Hyarogen-bonding and Van der Waals force it is stronger, to high containing cotton/wash fiber yarn adhesiveness, therefore film forming is stronger；It is swollen energy
The increase of power is also beneficial to the coating and film forming of slurries, therefore CS- α CD plasma membrane integrity improves, and enhances the coating property of yarn, hair
Plumage is reduced simultaneously, introduces the association that hydrophilic oligosaccharides inhibits starch molecule hydrogen bond, the work of plasticising is played to starch size
With, not only increase its to fiber surface sprawl and diffusivity, also improve the tough degree of starch Yu fiber bonding layer,
The wearability and strength and extension property for making sizing improve.The deliquescent raising of CS- α CD and the enhancing of rheological property help to improve starch
Mobility, permeability and the wetability of slurry, slurries thus increase to the degree that is impregnated with of yarn interior, can make between the fiber in yarn
Stronger cohesive force is obtained, therefore even if yam surface serous coat is destroyed, since saturability is stronger between fiber in yarn, therefore yarn
It may continue to bear external force and not broken, this is also the strength and the main original that significantly improves of wearability of CS- α CD sizing
Cause.The enhancing of anti-aging property is then conducive to improve the anti-gel characteristic of starch, reduces starch retrogradation, plays stable slurry and subtract
The effect of few sizing quality fluctuation.However when immobilized rate is excessive, the hydrophobicity of slurry is gradually highlighted, and water solubility deteriorates, gelatinization
Difficulty, therefore every slashing performance index also declines therewith.
CS- α CD has preferable biodegradable performance, and B/C ratio is slightly above CS, and is much higher than PVA-205, illustrates this
The CS- α CD of text preparation is a kind of biodegradable environment-friendly size, not will cause secondary pollution, is expected to become a kind of novel,
The green sizing material of alternative PVA.
Claims (2)
1. a kind of immobilized starch of alpha-cyclodextrin (CS- α CD), it is characterised in that the material quality of the starch forms number are as follows: corn
50 parts of starch；50 parts of alpha-cyclodextrin；20 parts of malic acid；7.5 parts of sodium hypophosphite；300 parts of deionized water, degree of substitution be 0.61~
0.66。
2. a kind of preparation method of the immobilized starch of alpha-cyclodextrin (CS- α CD), the preparation method is using α-ring described in claim 1
The material quality composition of the immobilized starch of dextrin (CS- α CD) and following processing step:
(1) starch suspension is made in the native cornstarch of the number, alpha-cyclodextrin and 200 parts of deionized waters, be transferred to
It in 500mL three-necked flask, is placed in 85 DEG C of water-baths, connects condensing unit, Heat Gelatinization 30min is then dripped by constant pressure
The solution of 100 parts of malic acid containing the number and sodium hypophosphite is added in liquid funnel, stirs evenly, mixture is transferred to baking
It is taken out after 120 DEG C of reaction 2h of case.
(2) take out and crush after reaction, be washed with deionized twice, then with 75% twice of ethanol washing, centrifugation dries
It is dry to obtain the immobilized starch of sample alpha-cyclodextrin, that is, CS- α CD.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811193613.6A CN109293789A (en) | 2018-10-15 | 2018-10-15 | A kind of alpha-cyclodextrin modified starch paste and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811193613.6A CN109293789A (en) | 2018-10-15 | 2018-10-15 | A kind of alpha-cyclodextrin modified starch paste and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109293789A true CN109293789A (en) | 2019-02-01 |
Family
ID=65162632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811193613.6A Pending CN109293789A (en) | 2018-10-15 | 2018-10-15 | A kind of alpha-cyclodextrin modified starch paste and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109293789A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4253651A1 (en) * | 2022-03-31 | 2023-10-04 | Raiz - Instituto De Investigação Da Floresta E Papel | Method for coating cellulosic material |
-
2018
- 2018-10-15 CN CN201811193613.6A patent/CN109293789A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4253651A1 (en) * | 2022-03-31 | 2023-10-04 | Raiz - Instituto De Investigação Da Floresta E Papel | Method for coating cellulosic material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Heinze et al. | Cellulose derivatives: synthesis, structure, and properties | |
| US9725849B2 (en) | Method for pretreating cellulose pulp | |
| Han et al. | Preparation and comparative assessment of regenerated cellulose films from corn (Zea mays) stalk pulp fines in DMAc/LiCl solution | |
| LeCorre et al. | Influence of botanic origin and amylose content on the morphology of starch nanocrystals | |
| Mbougueng et al. | Influence of acetylation on physicochemical, functional and thermal properties of potato and cassava starches | |
| Gujral et al. | Synthesis, characterization, and utilization of potato starch nanoparticles as a filler in nanocomposite films | |
| Kambli et al. | Synthesis and characterization of microcrystalline cellulose powder from corn husk fibres using bio-chemical route | |
| Salam et al. | Incorporation of carboxyl groups into xylan for improved absorbency | |
| CN105061605A (en) | Modified polysaccharide with fluorescent property as well as preparation method and application thereof | |
| Valdespino-León et al. | Biodegradable electrosprayed pectin films: An alternative to valorize coffee mucilage | |
| CN110408057B (en) | DHPMC blending crosslinking modified collagen suitable for biomedicine and preparation method thereof | |
| Zhao et al. | Bio-based polymer colorants from nonaqueous reactive dyeing of regenerated cellulose for plastics and textiles | |
| Veelaert et al. | The gelation of dialdehyde starch | |
| CN109293789A (en) | A kind of alpha-cyclodextrin modified starch paste and preparation method thereof | |
| Zhang et al. | Biomass-based single-and double-network hydrogels derived from cellulose microfiber and chitosan for potential application as plant growing substrate | |
| Hollinger et al. | Thermodynamic aspects of the gelatinization and swelling of crosslinked starch | |
| Kahn | Characterization of starch isolated from avocado seeds | |
| Rahaman et al. | Utilization of waste textile cotton by synthesizing sodium carboxymethyl cellulose: an approach to minimize textile solid waste | |
| CN102936290B (en) | Acetylated corn starch and preparation method thereof | |
| Teli et al. | Application of germinated maize starch in textile printing | |
| NO140830B (en) | PROCEDURE FOR PREPARING A CARBOXYMETHYLELLELLOSE-CONTAINING FIBER SHEET PRODUCT | |
| CN107108758A (en) | For the method for the water-soluble cellulose derivative for producing the water-insoluble particle with reduction content | |
| WO2016075370A1 (en) | Cationic parenchymal cellulose | |
| Tang et al. | Synthesis of hydroxypropylated debranched pea starch with high substitution degree in an ionic liquid, and its characterization and properties | |
| Fei et al. | Effects of Premna microphylla turcz polysaccharide on rheological, gelling, and structural properties of mung bean starch and their interactions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190201 |